Slurry, polishing liquid set, polishing liquid, method for polishing substrate, and substrate

ABSTRACT

The polishing liquid according to the embodiment comprises abrasive grains, an additive and water, wherein the abrasive grains include a tetravalent metal element hydroxide, and produce a liquid phase with a nonvolatile content of 500 ppm or greater when an aqueous dispersion with a content of the abrasive grains adjusted to 1.0 mass % has been centrifuged for 50 minutes at a centrifugal acceleration of 1.59×10 5  G.

TECHNICAL FIELD

The present invention relates to a slurry, a polishing liquid set, apolishing liquid, a substrate polishing method, and a substrate. Inparticular, the invention relates to a slurry, a polishing liquid set, apolishing liquid, a substrate polishing method and a substrate, to beused in manufacturing steps for semiconductor elements.

BACKGROUND ART

In recent years, machining techniques for increasing density andmicronization are becoming ever more important in manufacturing stepsfor semiconductor elements. One such machining technique, chemicalmechanical polishing (CMP), has become an essential technique inmanufacturing steps for semiconductor elements, for formation of ShallowTrench Isolation (hereunder also referred to as “STI”), flattening ofpremetal dielectric layers and interlayer dielectric films, andformation of plugs and embedded metal wirings.

Fumed silica-based polishing liquids are commonly used in CMP duringconventional manufacturing steps for semiconductor elements, in order toflatten the insulating films such as silicon oxide films that are formedby methods such as CVD (Chemical Vapor Deposition) or spin coatingmethods. Fumed silica-based polishing liquids are produced by conductinggrain growth of abrasive grains by methods such as thermal decompositionwith silicon tetrachloride, and adjusting the pH. However, suchsilica-based polishing liquids have the technical problem of lowpolishing rate.

Incidentally, STI is used for device isolation on integrated circuits ingeneration devices starting from design rules of 0.25 μm. In STIformation, CMP is used to remove excess silicon oxide films afterformation on substrates. In order to halt polishing in CMP, a stopperfilm with a slow polishing rate is formed under the silicon oxide film.A silicon nitride film or polysilicon film is used for the stopper film,preferably with a high polishing selective ratio of the silicon oxidefilm with respect to the stopper film (polishing rate ratio: polishingrate on silicon oxide film/polishing rate on stopper film). Asilica-based polishing liquid such as a conventional colloidalsilica-based polishing liquid has a low polishing selective ratio ofabout 3 for the silicon oxide film with respect to the stopper film, andit tends not to have properties that can withstand practical use forSTI.

On the other hand, cerium oxide-based polishing liquids comprisingcerium oxide particles as abrasive grains are used as polishing liquidsfor glass surfaces such as photomasks or lenses. Cerium oxide-basedpolishing liquids have the advantage of faster polishing rate comparedto silica-based polishing liquids comprising silica particles as theabrasive grains, or alumina-based polishing liquids comprising aluminaparticles as the abrasive grains. In recent years, polishing liquids forsemiconductors, employing high-purity cerium oxide particles, have cometo be used as cerium oxide-based polishing liquids (see Patent document1, for example).

A variety of properties are required for polishing liquids such ascerium oxide-based polishing liquids. For example, it is required toincrease the dispersibility of the abrasive grains such as cerium oxideparticles, and to accomplish flat polishing of substrates withirregularities. Using STI as an example, there is a demand for improvingpolishing selective ratios for inorganic insulating films (such assilicon oxide films) as films to be polished, with respect to thepolishing rates for stopper films (such as silicon nitride films orpolysilicon films). Additives are often added to polishing liquids tomeet this demand. For example, there is known addition of additives topolishing liquids containing cerium oxide-based particles, to controlthe polishing rates of the polishing liquids and improve the globalflatness (see Patent document 2, for example).

Incidentally, as demand increases for achieving greater micronization ofwirings in recent manufacturing steps for semiconductor elements,scratches formed during polishing are becoming problematic.Specifically, when polishing using conventional cerium oxide-basedpolishing liquids, fine scratches have not posed problems so long as thesizes of the scratches are smaller than conventional wiring widths, butthey can be problematic when it is attempted to achieve greatermicronization of wirings.

A solution to this problem is being sought through studying polishingliquids that employ particles of tetravalent metal element hydroxides(see Patent document 3, for example). Methods for producing particles oftetravalent metal element hydroxides are also being studied (see Patentdocument 4, for example). Such techniques are aimed at reducingparticle-induced scratches, by maintaining the chemical action of thetetravalent metal element hydroxide particles while minimizing theirmechanical action.

CITATION LIST Patent Literature

-   [Patent document 1] Japanese Unexamined Patent Application    Publication HEI No. 10-106994-   [Patent document 2] Japanese Unexamined Patent Application    Publication HEI No. 08-022970-   [Patent Document 3] International Patent Publication No. WO02/067309-   [Patent document 4] Japanese Unexamined Patent Application    Publication No. 2006-249129

SUMMARY OF INVENTION Technical Problem

The techniques described in Patent documents 3 and 4, however, cannot besaid to provide sufficiently high polishing rate, despite reduction inscratches. Since polishing rate directly affects the efficiency of theproduction process, polishing liquids with higher polishing rates aredesired.

When the polishing liquid contains an additive, the effect obtained byadding the additive is often offset by reduced polishing rate, and ithas been difficult to achieve polishing rate together with additionalpolishing properties.

The present invention is directed toward solving the problems describedabove, and it is an object thereof to provide a slurry that allowspolishing of films at a superior polishing rate compared to conventionalpolishing liquids. It is another object of the invention to provide aslurry that can yield a polishing liquid that allows polishing of filmsat a superior polishing rate compared to conventional polishing liquidswhile allowing the addition effects of additives to be maintained.

It is yet another object of the invention to provide a polishing liquidset and polishing liquid that allow polishing of films at a superiorpolishing rate compared to conventional polishing liquids while allowingthe addition effects of additives to be maintained.

It is yet another object of the invention to provide a polishing methodusing the slurry, polishing liquid set or polishing liquid, and asubstrate obtained by the method.

Solution to Problem

The present inventors have conducted diligent research on slurries usingabrasive grains comprising tetravalent metal element hydroxides, and asa result, they have found that films can be polished at superiorpolishing rates compared to conventional polishing liquids, irrespectiveof the presence or absence of additives, by using abrasive grains thatproduce a liquid phase with a high nonvolatile content when an aqueousdispersion comprising the abrasive grains dispersed in water has beencentrifuged under specific conditions.

Specifically, the slurry of the invention comprises abrasive grains andwater, the abrasive grains including a tetravalent metal elementhydroxide, and producing a liquid phase with a nonvolatile content of500 ppm or greater when an aqueous dispersion with a content of theabrasive grains adjusted to 1.0 mass % has been centrifuged for 50minutes at a centrifugal acceleration of 1.59×10⁵ G. An aqueousdispersion with a content of the abrasive grains adjusted to aprescribed value is a liquid comprising the prescribed amount ofabrasive grains and water. Here, “ppm” represents ppm by mass, namely“parts per million mass”.

With a slurry according to the invention, when a polishing liquidobtained by adding an additive to the slurry is used, it is possible toaccomplish polishing of films at superior polishing rate compared toconventional polishing liquids, while maintaining the effects of addingthe additives. In addition, it is also possible to accomplish polishingof films with superior polishing rate compared to conventional polishingliquids, when a slurry according to the invention is used for polishingwithout addition of additives. Furthermore, with a slurry according tothe invention, it is possible to inhibit formation of scratches onpolished surfaces since the abrasive grains include a tetravalent metalelement hydroxide.

The present inventors have conducted further research on slurries usingabrasive grains comprising tetravalent metal element hydroxides, and asa result, they have found that films can be polished at even moresuperior polishing rates compared to conventional polishing liquids, byusing abrasive grains that have photoabsorption (absorbance) in aspecified range for light of a specific wavelength, in an aqueousdispersion comprising a specific amount of the abrasive grains.

In a slurry according to the invention, the abrasive grains preferablyproduce absorbance of 1.50 or greater for light with a wavelength of 400nm in an aqueous dispersion with a content of the abrasive grainsadjusted to 1.0 mass %. This allows polishing of films with even moresuperior polishing rate compared to conventional polishing liquids.

In a slurry according to the invention, the abrasive grains preferablyproduce absorbance of 1.000 or greater for light with a wavelength of290 nm in an aqueous dispersion with a content of the abrasive grainsadjusted to 0.0065 mass % (65 ppm). This allows polishing of films witheven more superior polishing rate compared to conventional polishingliquids.

In a slurry according to the invention, the abrasive grains preferablyproduce absorbance of not greater than 0.010 for light with a wavelengthof 450-600 nm in an aqueous dispersion with a content of the abrasivegrains adjusted to 0.0065 mass %. This allows polishing of films witheven more superior polishing rate compared to conventional polishingliquids.

The present inventors have conducted yet further research on slurriesusing abrasive grains comprising tetravalent metal element hydroxides,and as a result, they have found that films can be polished at even moresuperior polishing rates compared to conventional polishing liquids, byusing abrasive grains that can increase the light transmittance forlight with a specific wavelength, in an aqueous dispersion comprising aspecific amount of the abrasive grains. That is, in a slurry accordingto the invention, the abrasive grains preferably produce lighttransmittance of 50%/cm or greater for light with a wavelength of 500 nmin an aqueous dispersion with a content of the abrasive grains adjustedto 1.0 mass %.

The tetravalent metal element hydroxide is preferably obtained by mixinga tetravalent metal element salt and an alkali solution. This will allowparticles with extremely fine particle sizes to be obtained as abrasivegrains, thus further improving the effect of reducing scratches.

The tetravalent metal element is preferably tetravalent cerium. Thiswill yield fine particles with high chemical activity as abrasivegrains, and will therefore allow polishing of films with even moresuperior polishing rate compared to conventional polishing liquids.

The present inventors have found that, for a polishing liquid comprisingadditives in addition to the constituent components of the slurry, thereduction in polishing rate for films that occurs with addition of theadditives can be avoided by using abrasive grains that produce a liquidphase with a high nonvolatile content when an aqueous dispersioncomprising the abrasive grains dispersed in water has been centrifugedunder specific conditions.

Specifically, a polishing liquid set according to the inventioncomprises the constituent components of a polishing liquid separatelystored as a first liquid and second liquid, so that the first liquid andsecond liquid are mixed to form the polishing liquid, the first liquidbeing the aforementioned slurry, and the second liquid comprising anadditive and water. With the polishing liquid set of the invention, itis possible to accomplish polishing of films at a superior polishingrate compared to conventional polishing liquids, while maintaining theeffects of adding additives. The polishing liquid set of the inventioncan inhibit formation of scratches.

The additive is preferably at least one selected from the groupconsisting of vinyl alcohol polymers and derivatives of the vinylalcohol polymers. In this case, the additive will cover the abrasivegrain surfaces to inhibit adhesion of the abrasive grains onto thesurface to be polished, thereby improving the dispersibility of theabrasive grains and improving the stability of the polishing liquid. Itcan also improve the cleanability of the polished surface.

The content of the additive is preferably 0.01 mass % or greater basedon the total mass of the polishing liquid. This will allow polishing offilms with even more superior polishing rate compared to conventionalpolishing liquids, while allowing the effect of the additives to beobtained.

Also, the polishing liquid of the invention comprises abrasive grains,an additive and water, the abrasive grains including a tetravalent metalelement hydroxide, and producing a liquid phase with a nonvolatilecontent of 500 ppm or greater when an aqueous dispersion with a contentof the abrasive grains adjusted to 1.0 mass % has been centrifuged for50 minutes at a centrifugal acceleration of 1.59×10⁵ G.

With the polishing liquid of the invention, it is possible to accomplishpolishing of films at a superior polishing rate compared to conventionalpolishing liquids, while maintaining the effects of adding additives.Furthermore, with a polishing liquid of the invention, it is possible toinhibit formation of scratches on polished surfaces since the abrasivegrains include a tetravalent metal element hydroxide.

In a polishing liquid of the invention, the abrasive grains preferablyproduce absorbance of 1.50 or greater for light with a wavelength of 400nm in an aqueous dispersion with a content of the abrasive grainsadjusted to 1.0 mass %. This allows polishing of films with even moresuperior polishing rate compared to conventional polishing liquids.

In a polishing liquid of the invention, the abrasive grains preferablyproduce absorbance of 1.000 or greater for light with a wavelength of290 nm in an aqueous dispersion with a content of the abrasive grainsadjusted to 0.0065 mass %. This allows polishing of films with even moresuperior polishing rate compared to conventional polishing liquids.

In a polishing liquid of the invention, the abrasive grains preferablyproduce absorbance of not greater than 0.010 for light with a wavelengthof 450-600 nm in an aqueous dispersion with a content of the abrasivegrains adjusted to 0.0065 mass %. This allows polishing of films witheven more superior polishing rate compared to conventional polishingliquids.

In a polishing liquid of the invention, the abrasive grains preferablyproduce light transmittance of 50%/cm or greater for light with awavelength of 500 nm in an aqueous dispersion with a content of theabrasive grains adjusted to 1.0 mass %. This will make it possible toeasily obtain both a superior polishing rate and the effects of addingadditives compared to conventional polishing liquids.

The tetravalent metal element hydroxide in the polishing liquid of theinvention is preferably obtained by mixing a tetravalent metal elementsalt and an alkali solution. This will allow particles with extremelyfine particle sizes to be obtained as abrasive grains, thus a polishingliquid with an even more excellent effect of reducing scratches can beobtained.

The tetravalent metal element in the polishing liquid of the inventionis preferably tetravalent cerium. This yields fine particles with highchemical activity as abrasive grains, and therefore allows polishing offilms with even more superior polishing rate compared to conventionalpolishing liquids.

The additive in the polishing liquid of the invention is preferably atleast one selected from the group consisting of vinyl alcohol polymersand derivatives of the vinyl alcohol polymers. In this case, theadditive will cover the abrasive grain surfaces to inhibit adhesion ofthe abrasive grains onto the surface to be polished, thereby improvingthe dispersibility of the abrasive grains and improving the stability ofthe polishing liquid. It can also improve the cleanability of thepolished surface.

The content of the additive in the polishing liquid of the invention ispreferably 0.01 mass % or greater based on the total mass of thepolishing liquid. This will allow polishing of films with even moresuperior polishing rate compared to conventional polishing liquids,while allowing the effects of the additives to be obtained.

The invention further provides a substrate polishing method using theaforementioned slurry, polishing liquid set or polishing liquid. Thepolishing method allows polishing of films at a superior polishing ratecompared to conventional polishing methods. In addition, the polishingmethod can inhibit formation of scratches and yield a substrate withexcellent flatness.

A first embodiment of the polishing method of the invention is apolishing method employing the aforementioned slurry. Specifically, thepolishing method of the first embodiment comprises a step of placing afilm to be polished, of a substrate which has the film to be polished onits surface, so as to face an abrasive pad, and a step of polishing atleast a portion of the film to be polished while supplying theaforementioned slurry between the abrasive pad and the film to bepolished.

Second and third embodiments of the polishing method of the inventionare polishing methods using the aforementioned polishing liquid set.These polishing methods can avoid the problems of abrasive grainaggregation and changes in polishing properties, which are concerns withprolonged storage after mixture of additives.

Specifically, the polishing method of the second embodiment comprises astep of placing a film to be polished, of a substrate which has the filmto be polished on its surface, so as to face an abrasive pad, a step ofmixing the first liquid and second liquid of the aforementionedpolishing liquid set to obtain a polishing liquid, and a step ofpolishing at least a portion of the film to be polished while supplyingthe polishing liquid between the abrasive pad and the film to bepolished. The substrate polishing method of the third embodimentcomprises a step of placing a film to be polished, of a substrate whichhas the film to be polished on its surface, so as to face an abrasivepad, and a step of polishing at least a portion of the film to bepolished while respectively supplying both the first liquid and secondliquid of the polishing liquid set between the abrasive pad and the filmto be polished.

A fourth embodiment of the polishing method of the invention is apolishing method employing the aforementioned polishing liquid.Specifically, the polishing method of the fourth embodiment comprises astep of placing a film to be polished, of a substrate which has the filmto be polished on its surface, so as to face an abrasive pad, and a stepof polishing at least a portion of the film to be polished whilesupplying the aforementioned polishing liquid between the abrasive padand the film to be polished.

The film to be polished preferably includes silicon oxide. The surfaceof the film to be polished preferably has irregularities. Thesepolishing methods allow the characteristics of the polishing liquid tobe adequately exhibited.

The substrate of the invention is one that has been polished by theaforementioned polishing method.

Advantageous Effects of Invention

With the slurry of the invention, it is possible to accomplish polishingof a film to be polished at a superior polishing rate compared to aconventional polishing liquid. With the slurry of the invention, it isalso possible to obtain a polishing liquid that allows polishing offilms at a superior polishing rate compared to conventional polishingliquids, while maintaining the effects of adding additives. Also, withthe polishing liquid set and polishing liquid of the invention, it ispossible to accomplish polishing of films at a superior polishing ratecompared to conventional polishing liquids, while maintaining theeffects of adding additives. The polishing method of the invention hasexcellent throughput since it allows polishing of films at superiorpolishing rate, while permitting desired properties (such as flatnessand selectivity) to be obtained when using additives.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 is a schematic cross-sectional view of an example of an anglerotor.

FIG. 2 is a schematic diagram showing the aggregated condition ofabrasive grains when an additive has been added.

FIG. 3 is a schematic diagram showing the aggregated condition ofabrasive grains when an additive has been added.

FIG. 4 is a figure showing the relationship between nonvolatile contentof supernatant liquid and polishing rate.

FIG. 5 is a figure showing the relationship between absorbance for lightwith a wavelength of 290 nm and polishing rate.

FIG. 6 is a figure showing the relationship between absorbance for lightwith a wavelength of 400 nm and polishing rate.

FIG. 7 is a figure showing the relationship between absorbance for lightwith a wavelength of 290 nm and absorbance for light with a wavelengthof 400 nm.

DESCRIPTION OF EMBODIMENTS

Embodiments of the invention will now be explained in detail.

<Polishing Liquid>

The polishing liquid of this embodiment comprises at least abrasivegrains, an additive and water. Each of these constituent components willnow be explained.

(Abrasive Grains)

The abrasive grains include a tetravalent metal element hydroxide. Thetetravalent metal element is preferably a rare earth element, and fromthe viewpoint of facilitating formation of a hydroxide suitable forpolishing, it is more preferably at least one kind selected from thegroup consisting of scandium, yttrium, lanthanum, cerium, praseodymium,neodymium, promethium, gadolinium, terbium, dysprosium, holmium, erbium,thulium, ytterbium and lutetium. The tetravalent metal element is evenmore preferably cerium, from the viewpoint of ready availability and amore superior polishing rate.

The abrasive grains are preferably composed of a tetravalent metalelement hydroxide, and from the viewpoint of high chemical activity anda more superior polishing rate, they are more preferably composed of ahydroxide of tetravalent cerium. The polishing liquid of this embodimentmay also combine other types of abrasive grains, within ranges that donot impair the properties of the abrasive grains including thetetravalent metal element hydroxide. Specifically, abrasive grains ofsilica, alumina or zirconia, for example, may be used.

The content of the tetravalent metal element hydroxide in the abrasivegrains is preferably 50 mass % or greater, more preferably 60 mass % orgreater, even more preferably 70 mass % or greater, especially morepreferably 80 mass % or greater and extremely preferably 90 mass % orgreater, based on the total mass of the abrasive grains.

Of the constituent components of the polishing liquid of thisembodiment, the tetravalent metal element hydroxide is believed to havea major effect on the polishing properties. Thus, adjusting the contentof the tetravalent metal element hydroxide can improve chemicalinteraction between the abrasive grains and surface to be polished, andfurther improve the polishing rate. Specifically, the content of thetetravalent metal element hydroxide is preferably 0.01 mass % orgreater, more preferably 0.05 mass % or greater and even more preferably0.1 mass % or greater based on the total mass of the polishing liquid,from the viewpoint of helping to sufficiently exhibit the function ofthe tetravalent metal element hydroxide. In addition, the content of thetetravalent metal element hydroxide is preferably not greater than 8mass % and more preferably not greater than 5 mass % based on the totalmass of the polishing liquid, from the viewpoint of helping to avoidaggregation of the abrasive grains.

The abrasive grain content is not particularly restricted, but from theviewpoint of helping to avoid aggregation of the abrasive grains andallowing the abrasive grains to effectively act on the surface to bepolished to smoothly promote polishing, it is preferably 0.01-10 mass %and more preferably 0.1-5 mass % based on the total mass of thepolishing liquid.

The mean secondary particle size of the abrasive grains (hereunderreferred to as “mean particle size”, unless otherwise specified) ispreferably 1-200 nm from the viewpoint of obtaining a more superiorpolishing rate. Since a smaller mean particle size to some extentincreases the specific surface area of the abrasive grains that contactwith the surface to be polished, and thus allowing the polishing rate tofurther improved, the mean particle size is more preferably not greaterthan 150 nm, even more preferably not greater than 100 nm, especiallymore preferably not greater than 80 nm and extremely preferably notgreater than 50 nm. Since a larger mean particle size to some extenttends to facilitate increase in the polishing rate, the mean particlesize is more preferably at least 2 nm and even more preferably at least5 nm.

The mean particle size of the abrasive grains can be measured with aparticle size distribution meter based on the photon correlation method,and specifically, it may be measured using a Zetasizer 3000HS by MalvernInstruments Ltd. or an N5 by Beckman Coulter, Inc., for example.Specifically, in a measuring method using a Zetasizer 3000HS, forexample, an aqueous dispersion with the content of the abrasive grainsadjusted to 0.2 mass % is prepared, and approximately 4 mL (where Lrepresents “liters”, same hereunder) of the aqueous dispersion is pouredinto a 1 cm-square cell, and the cell is placed in the apparatus.Measurement is conducted at 25° C. with a dispersing medium refractiveindex of 1.33 and a viscosity of 0.887 mPa·s, and the value representedas Z-average Size is read as the mean particle size of the abrasivegrains.

[Nonvolatile Content]

The abrasive grains are believed to comprise large particles withparticle sizes that can be measured with a particle size distributionmeter, and fine particles with particle sizes that cannot be measuredwith a particle size distribution meter. When an aqueous dispersioncomprising such abrasive grains dispersed in water has been centrifugedby the action of sufficient centrifugal force, the aqueous dispersionundergoes mainly solid-liquid separation into the precipitate and thesupernatant liquid (liquid phase), with the large particles settling asthe precipitate and the fine particles floating up into the supernatantliquid.

The present inventors have found that films can be polished at superiorpolishing rates compared to conventional polishing liquids, by usingabrasive grains that can produce a supernatant liquid with a highnonvolatile content when an aqueous dispersion comprising a sufficientamount of the abrasive grains has been centrifuged under conditions thatallow action of centrifugal force that can adequately separate the largeparticles and fine particles. Specifically, the abrasive grains of thisembodiment produce a supernatant liquid with a nonvolatile content of500 ppm or greater when an aqueous dispersion with a content of theabrasive grains adjusted to 1.0 mass % has been centrifuged for 50minutes at a centrifugal acceleration of 1.59×10⁵ G.

The present inventors conjecture the following as the reason for whichan effect of improving polishing rate is obtained when the nonvolatilecontent of the centrifuged supernatant liquid is high. A highnonvolatile content means that the proportion of fine particles is high,and presumably an increased nonvolatile content enlarges the surfacearea of the abrasive grains contacting with the surface to be polished.It is thought that this promotes polishing by chemical action, andimproves the polishing rate compared to the prior art.

The nonvolatile content of the supernatant liquid is preferably 1000 ppmor greater, more preferably 1500 ppm or greater, even more preferably2000 ppm or greater and especially preferably 3000 ppm or greater, fromthe viewpoint of obtaining an even more superior polishing rate. Theupper limit for the nonvolatile content of the supernatant liquid is notparticularly restricted, for the reasons explained above, and it may be100000 ppm, for example.

The apparatus used for the centrifugal separation may be an angle rotorhaving a tube positioned at a prescribed angle, or a swing rotor havinga variable tube angle, with the tube positioned horizontally or nearlyhorizontally during the centrifugal separation.

FIG. 1 is a schematic cross-sectional view of an example of an anglerotor. The angle rotor 1 has bilateral symmetry around rotation axis A1as the center, and only one side (the left side) is shown in FIG. 1while the other side (the right side) is omitted. In FIG. 1, A2 is thetube angle, R_(min) is the minimum radius from the rotation axis A1 tothe tube, and R_(max) is the maximum radius from the rotation axis A1 tothe tube. R_(av) is the average radius from the rotation axis A1 to thetube, and is calculated as “(R_(min)+R_(max))/2”.

For this type of centrifugal separation apparatus, the centrifugalacceleration [units: G] can be calculated by the following formula (1).

Centrifugal acceleration [G]=1118×R×N ²×10⁻⁸  (1)

(In the formula, R represents the radius of rotation (cm), and Nrepresents the rotational speed per minute (rpm=revolutions perminute).)

For this embodiment, centrifugal separation is carried out with therotational speed N set for a centrifugal acceleration of 1.59×10⁵ Gusing the value of the average radius R_(av) in FIG. 1 as the radius ofrotation R in formula (1). When a swing rotor is to be used instead ofan angle rotor as shown in FIG. 1, the minimum radius R_(min), maximumradius R_(max) and average radius R_(av) are each calculated from thestate of the tube in the centrifugal separation, to set the conditions.

The abrasive grains may be separated into large particles and fineparticles using a 70P-72 ultracentrifuge by Hitachi Koki Co., Ltd., forexample, as the angle rotor. Specifically, centrifugal separation of theaqueous dispersion using a 70P-72 may be carried out in the followingmanner, as an example. First, an aqueous dispersion with a content ofthe abrasive grain adjusted to 1.0 mass % is prepared, and after fillingit into a centrifuge tube, the centrifuge tube is placed in a rotor.After rotating for 50 minutes at a rotational speed of 50000 rpm, thecentrifuge tube is removed from the rotor and the supernatant liquid inthe centrifuge tube is collected. The nonvolatile content of thesupernatant liquid can be calculated by measuring the mass of thecollected supernatant liquid and the mass of the residue after dryingthe supernatant liquid.

[Absorbance]

The abrasive grains preferably satisfy either or both of the followingconditions (a) and (b).

(a) The abrasive grains produce absorbance of 1.50 or greater for lightwith a wavelength of 400 nm in an aqueous dispersion with a content ofthe abrasive grains adjusted to 1.0 mass %.

(b) The abrasive grains produce absorbance of 1.000 or greater for lightwith a wavelength of 290 nm in an aqueous dispersion with a content ofthe abrasive grains adjusted to 0.0065 mass %.

The present inventors have found that films can be polished at even moresuperior polishing rate compared to conventional polishing liquids, byusing abrasive grains satisfying the aforementioned conditions forabsorbance of light with a wavelength of 290 nm and/or with a wavelengthof 400 nm. The present inventors further found that a polishing liquidand slurry satisfying these conditions have a slight yellowish tint asobserved visually, and that a greater degree of yellowishness of thepolishing liquid and slurry is linked to more superior polishing rate.

In regard to condition (a), it is not necessarily fully understood whyan effect of improving polishing rate is obtained by using abrasivegrains that produce absorbance of at least 1.50 for light with awavelength of 400 nm in an aqueous dispersion with a content of theabrasive grains adjusted to 1.0 mass %, but the present inventorsconjecture as follows. Specifically, depending on the conditions forproduction of the tetravalent metal element hydroxide (M(OH)₄), it isbelieved that particles of M(OH)₃X, composed of a tetravalent metal(M⁴⁺), 3 hydroxyl groups (OH) and one anion (X), are produced for someof the abrasive grains. In M(OH)₃X, the electron-withdrawing anion (X⁻)acts to improve the reactivity of the hydroxyl groups, and an increasingabundance of M(OH)₃X is thought to lead to improved polishing rate.Also, since the M(OH)₃X particles absorb light with a wavelength of 400nm, presumably an increased abundance of M(OH)₃X causes increasedabsorbance for light with a wavelength of 400 nm, and improves thepolishing rate.

The absorption peak of M(OH)₃X at a wavelength of 400 nm has beenconfirmed to be much lower than the absorption peak at a wavelength of290 nm. In this regard, as a result of studying degrees of absorbanceusing aqueous dispersions with relatively high abrasive grain contentsof 1.0 mass %, which allow absorbance to be easily detected as highabsorbance, the present inventors have found that the effect ofimproving polishing rate is superior when using abrasive grains thatproduce absorbance of at least 1.50 for light with a wavelength of 400nm in the aqueous dispersion. Incidentally, since it is thought that theabsorbance for light with a wavelength of 400 nm derives from theabrasive grains, as explained above, naturally it would not be possibleto polish a film at a superior polishing rate with a polishing liquidcomprising a substance (such as a pigment component exhibiting a yellowcolor) that produces absorbance of at least 1.50 for light with awavelength of 400 nm, instead of abrasive grains that produce absorbanceof at least 1.50 for light with a wavelength of 400 nm.

The absorbance for light with a wavelength of 400 nm is more preferably2.00 or greater, even more preferably 2.50 or greater and especiallypreferably 3.00 or greater, from the viewpoint of allowing polishing offilms at an even more superior polishing rate. The upper limit for theabsorbance for light with a wavelength of 400 nm is not particularlyrestricted, but is preferably 10.0, for example.

In regard to condition (b), it is not necessarily fully understood whyan effect of improving polishing rate is obtained by using abrasivegrains that produce absorbance of 1.000 or greater for light with awavelength of 290 nm in an aqueous dispersion with a content of theabrasive grains adjusted to 0.0065 mass %, but the present inventorsconjecture as follows. Specifically, particles of M(OH)₃X that areproduced depending on the production conditions for the tetravalentmetal element hydroxide (M(OH)₄) have a calculated absorption peak at awavelength of about 290 nm, and for example, particles composed ofCe⁴⁺(OH⁻)₃NO₃ ⁻ have an absorption peak at a wavelength of 290 nm.Consequently, it is believed that the polishing rate is improved inaccordance with the increase in absorbance for light with a wavelengthof 290 nm due to the increase in the abundance of M(OH)₃X.

The absorbance for light with a wavelength of about 290 nm tends to bedetected to a greater degree as the measuring limit is exceeded. In thisregard, as a result of studying degrees of absorbance using aqueousdispersions with relatively low abrasive grain contents of 0.0065 mass%, which allow absorbance to be easily detected as low absorbance, thepresent inventors have found that the effect of improving polishing rateis superior when using abrasive grains that produce absorbance of atleast 1.000 for light with a wavelength of 290 nm in the aqueousdispersion. The present inventors have also found that, apart from lightwith a wavelength of about 400 nm, which when absorbed by an absorbingsubstance tends to cause the absorbing substance to exhibit a yellowcolor, higher absorbance of abrasive grains for light with a wavelengthof about 290 nm produces deeper yellowishness in a polishing liquid orslurry employing such abrasive grains. Specifically, the presentinventors found that the absorbance for light with a wavelength of 290nm in an aqueous dispersion with an abrasive grain content of 0.0065mass % and the absorbance for light with a wavelength of 400 nm in anaqueous dispersion with an abrasive grain content of 1.0 mass % are verywell correlated, as shown in FIG. 6 described below.

The absorbance for light with a wavelength of 290 nm is more preferably1.050 or greater, even more preferably 1.100 or greater, especially morepreferably 1.200 or greater and extremely preferably 1.300 or greater,from the viewpoint of allowing polishing of films at an even moresuperior polishing rate. The upper limit for the absorbance for lightwith a wavelength of 290 nm is not particularly restricted, but ispreferably 10.00, for example.

From the viewpoint of polishing of films at an even more superiorpolishing rate with a polishing liquid of this embodiment, the abrasivegrains are preferably ones that produce absorbance of at least 1.50 forlight with a wavelength of 400 nm in an aqueous dispersion with acontent of the abrasive grains adjusted to 1.0 mass %, while alsoproducing absorbance of at least 1.000 for light with a wavelength of290 nm in an aqueous dispersion with a content of the abrasive grainsadjusted to 0.0065 mass %.

Also, the aforementioned metal hydroxides (M(OH)₄ and M(OH)₃X) tend notto exhibit absorption for light with wavelengths of 450 nm and greater,and especially for light with wavelengths of 450-600 nm. Therefore, fromthe viewpoint of minimizing adverse effects on polishing by the presenceof impurities, the abrasive grains preferably produce absorbance of notgreater than 0.010 for light with a wavelength of 450-600 nm in anaqueous dispersion with a content of the abrasive grains adjusted to0.0065 mass % (65 ppm). Specifically, the absorbance preferably does notexceed 0.010 for all light within a wavelength range of 450-600 nm in anaqueous dispersion with a content of the abrasive grains adjusted to0.0065 mass %. The absorbance for light with a wavelength of 450-600 nmis more preferably not greater than 0.005 and even more preferably notgreater than 0.001. The lower limit for the absorbance for light with awavelength of 450-600 nm is preferably 0.

The absorbance in an aqueous dispersion can be measured, for example,using a spectrophotometer (model name: U3310) by Hitachi, Ltd.Specifically, an aqueous dispersion with a content of the abrasivegrains adjusted to 0.0065 mass % or 1.0 mass % is prepared as ameasuring sample. Approximately 4 mL of the measuring sample is placedin a 1 cm-square cell, and the cell is set in the apparatus.Spectrophotometry is then conducted in a wavelength range of 200-600 nm,and the absorbance is judged from the obtained chart.

If absorbance of at least 1.000 is exhibited when the absorbance forlight with a wavelength of 290 nm is measured with excessive dilution sothat the abrasive grain content in the measuring sample is lower than0.0065 mass %, it is clear that the absorbance will also be at least1.000 when the abrasive grain content is 0.0065 mass %. Thus, theabsorbance may be screened by measuring the absorbance using an aqueousdispersion excessively diluted so that the abrasive grain content islower than 0.0065 mass %.

Screening of the absorbance may also be accomplished by assuming that ifabsorbance of at least 1.50 is exhibited when the absorbance for lightwith a wavelength of 400 nm is measured with excessive dilution so thatthe abrasive grain content is lower than 1.0 mass %, the absorbance willalso be at least 1.50 when the abrasive grain content is 1.0 mass %.Also, screening of the absorbance may be accomplished by assuming thatif absorbance of not greater than 0.010 is exhibited when the absorbancefor light with a wavelength of 450-600 nm is measured with dilution sothat the abrasive grain content is greater than 0.0065 mass %, theabsorbance will also be not greater than 0.010 when the abrasive graincontent is 0.0065 mass %.

[Light Transmittance]

The polishing liquid of this embodiment preferably has high transparencyfor visible light (it is visually transparent or nearly transparent).Specifically, the abrasive grains of the polishing liquid of thisembodiment preferably produce light transmittance of at least 50%/cm forlight with a wavelength of 500 nm in an aqueous dispersion with acontent of the abrasive grains adjusted to 1.0 mass %. This will help toreliably obtain an effect of improving the polishing rate based on thenonvolatile content as the index, as well as an effect of improvedpolishing rate based on absorbance as the index, and since reduction inpolishing rate by addition of additives can be further inhibited, itbecomes easier to obtain other properties while maintaining polishingrate. From this viewpoint, the light transmittance is more preferably atleast 60%/cm, even more preferably at least 70%/cm, especially morepreferably at least 80%/cm and extremely preferably at least 90%/cm. Theupper limit for the light transmittance is 100%/cm.

Although the reason for which reduction in polishing rate can beinhibited by adjusting the light transmittance of the abrasive grains isnot thoroughly understood, the present inventors conjecture as follows.The action exhibited as abrasive grains by the tetravalent metal elementhydroxide particles, such as cerium hydroxide particles, is thought todepend more on chemical action than on mechanical action. Therefore, thenumber of abrasive grains is believed to contribute to the polishingrate more than the sizes of the abrasive grains.

In the case of low light transmittance in an aqueous dispersion havingan abrasive grain content of 1.0 mass %, the abrasive grains present inthe aqueous dispersion presumably have relatively more particles withlarge particle sizes (hereunder referred to as “coarse particles”). Whenan additive (such as polyvinyl alcohol (PVA)) is added to a polishingliquid comprising such abrasive grains, other particles aggregate aroundthe coarse particles as nuclei, as shown in FIG. 2. As a result, thenumber of abrasive grains acting on the surface to be polished per unitarea (the effective abrasive grain number) is reduced and the specificsurface area of the abrasive grains contacting with the surface to bepolished is reduced, whereby presumably reduction in the polishing rateoccur.

Conversely, in the case of high light transmittance in an aqueousdispersion having an abrasive grain content of 1.0 mass %, the abrasivegrains present in the aqueous dispersion presumably are in the state offewer “coarse particles”. In such cases with a low abundance of coarseparticles, few coarse particles are available as nuclei for aggregation,and therefore aggregation between abrasive grains is inhibited or thesizes of the aggregated particles are smaller than the aggregatedparticles shown in FIG. 2, even when an additive (such as polyvinylalcohol) is added to the polishing liquid, as shown in FIG. 3. As aresult, the number of abrasive grains acting on the surface to bepolished per unit area (the effective abrasive grain number) ismaintained and the specific surface area of the abrasive grainscontacting with the surface to be polished is maintained, wherebypresumably reduction in the polishing rate does not easily occur.

According to research by the present inventors, it was found that evenamong polishing liquids having identical particle sizes to each other asmeasured with a common particle size measuring apparatus, some may bevisually transparent (high light transmittance) and some visually turbid(low light transmittance). This suggests that coarse particles, whichproduce the action described above, contribute to reduced polishing rateeven in slight amounts that cannot be detected with common particle sizemeasuring apparatuses.

It was also found that even repeated filtration to reduce the amount ofcoarse particles does not significantly improve the phenomenon ofreduced polishing rate with addition of additives, and in some cases theaforementioned effect of improving polishing rate due to absorbance isnot adequately exhibited. The present inventors found that this problemcan be overcome by using abrasive grains with high light transmittancein aqueous dispersion, by modifying the method for producing theabrasive grains, for example.

The light transmittance is the transmittance for light with a wavelengthof 500 nm. The light transmittance is measured with a spectrophotometer,and specifically, it is measured with an U3310 Spectrophotometer(apparatus name) by Hitachi, Ltd., for example.

As a more specific measuring method, an aqueous dispersion with acontent of the abrasive grains adjusted to 1.0 mass % is prepared as ameasuring sample. Approximately 4 mL of the measuring sample is placedin a 1 cm-square cell, the cell is set in the apparatus, and measurementis conducted. If the light transmittance is at least 50%/cm in anaqueous dispersion having an abrasive grain content of greater than 1.0mass %, it is clear that the light transmittance will also be at least50%/cm when the measuring sample is diluted to 1.0 mass %. Therefore,using an aqueous dispersion with an abrasive grain content of greaterthan 1.0 mass % allows screening of the light transmittance by aconvenient method.

[Method for Production of Abrasive Grains]

The tetravalent metal element hydroxide is preferably produced by mixinga tetravalent metal element salt (metal salt) and an alkali solution.This will allow particles with extremely fine particle sizes to beobtained, whereby a polishing liquid with an even more excellent effectof reducing scratches can be obtained. This method is disclosed inPatent document 4, for example. The tetravalent metal element hydroxidemay be obtained by mixing an aqueous solution of a tetravalent metalelement salt and an alkali solution. Examples of tetravalent metalelement salts include M(SO₄)₂, M(NH₄)₂(NO₃)₆ and M(NH₄)₄(SO₄)₄, where Mis the metal.

The means for adjusting the absorbance or light transmittance may beoptimization of the method for producing the tetravalent metal elementhydroxide. The method of altering the absorbance for light with awavelength of 400 nm or a wavelength of 290 nm may be, specifically,selecting the base in the alkali solution, adjusting the startingconcentrations of the metal salt aqueous solution and the alkalisolution, or adjusting the mixing rate of the metal salt aqueoussolution and the alkali solution. The method of altering the lighttransmittance for light with a wavelength of 500 nm may be,specifically, adjusting the starting concentrations of the metal saltaqueous solution and the alkali solution, adjusting the mixing rate ofthe metal salt aqueous solution and the alkali solution, adjusting thestirring speed for mixing, or adjusting the liquid temperature duringmixing.

In order to increase the absorbance for light with a wavelength of 400nm or a wavelength of 290 nm, and to increase the light transmittancefor light with a wavelength of 500 nm, the method for producing thetetravalent metal element hydroxide is preferably more “moderate”. Amethod of controlling the absorbance and light transmittance will now beexplained in greater detail.

{Alkali Solution}

The base to be used as an alkaline source in the alkali solution (suchas an aqueous alkali solution) is not particularly restricted, butspecific examples include organic bases such as ammonia, triethylamine,pyridine, piperidine, pyrrolidine, imidazole and chitosan and inorganicbases such as potassium hydroxide and sodium hydroxide. These bases maybe used alone or in combinations of two or more.

From the viewpoint of further inhibiting rapid reaction and furtherincreasing the absorbance for light with a wavelength of 400 nm and awavelength of 290 nm, the alkali solution used is preferably an alkalisolution exhibiting weak basicity. Of the bases mentioned above,nitrogen-containing heterocyclic organic bases are preferred, pyridine,piperidine, pyrrolidine and imidazole are more preferred, and pyridineand imidazole are even more preferred.

{Concentration}

The absorbance for light with a wavelength of 400 nm or a wavelength of290 nm, and the light transmittance for light with a wavelength of 500nm, can be altered by controlling the starting concentrations of themetal salt aqueous solution and the alkali solution. Specifically, theabsorbance and light transmittance tend to be higher with reducedprogression of the reaction between the acid and alkali per unit time,and for example, the absorbance and light transmittance tend to behigher with increased concentration of the metal salt aqueous solution,while the absorbance and light transmittance tend to be higher withreduced concentration of the alkali solution. When a nitrogen-containingheterocyclic organic base or the like exhibiting weak basicity is usedas the base, the alkali solution concentration is preferably higher thanwhen ammonia is used, from the viewpoint of productivity.

From the viewpoint of a gentler rise in pH, the metal salt concentrationof the tetravalent metal element salt in the metal salt aqueous solutionis preferably 0.010 mol/L or greater, more preferably 0.020 mol/L orgreater and even more preferably 0.030 mol/L or greater, based on thetotal metal salt aqueous solution. There is no particular restriction onthe upper limit for the metal salt concentration of the tetravalentmetal element, but for easier manageability, it is preferably notgreater than 1.000 mol/L based on the total metal salt aqueous solution.

From the viewpoint of a gentler rise in pH, the alkaline concentrationof the alkali solution is preferably not greater than 15.0 mol/L, morepreferably not greater than 12.0 mol/L and even more preferably notgreater than 10.0 mol/L or greater, based on the total alkali solution.There is no particular restriction on the lower limit for the alkalisolution, but from the viewpoint of productivity, it is preferably atleast 0.001 mol/L based on the total alkali solution.

The alkaline concentration of the alkali solution is preferably adjustedas appropriate depending on the type of alkali selected. For example,for an alkali with a pKa in the range of 20 or greater, the alkalineconcentration is preferably not greater than 0.1 mol/L, more preferablynot greater than 0.05 mol/L and even more preferably not greater than0.01 mol/L based on the total alkali solution, from the viewpoint of agentler rise in pH. There is no particular restriction on the lowerlimit for the alkali solution, but from the viewpoint of productivity,it is preferably at least 0.001 mol/L based on the total alkalisolution.

For an alkali with a pKa in the range of 12 or greater and less than 20,the alkaline concentration is preferably not greater than 1.0 mol/L,more preferably not greater than 0.5 mol/L and even more preferably notgreater than 0.1 mol/L based on the total alkali solution, from theviewpoint of a gentler rise in pH. There is no particular restriction onthe lower limit for the alkali solution, but from the viewpoint ofproductivity, it is preferably at least 0.01 mol/L based on the totalalkali solution.

For an alkali with a pKa in the range of less than 12, the alkalineconcentration is preferably not greater than 15.0 mol/L, more preferablynot greater than 10.0 mol/L and even more preferably not greater than5.0 mol/L based on the total alkali solution, from the viewpoint of agentler rise in pH. There is no particular restriction on the lowerlimit for the alkali solution, but from the viewpoint of productivity,it is preferably at least 0.1 mol/L based on the total alkali solution.

Specific examples of alkalis with pKa values in these ranges include1,8-diazabicyclo[5.4.0]undec-7-ene (pKa: 25) as an alkali with a pKa of20 or greater, potassium hydroxide (pKa: 16) and sodium hydroxide (pKa:13) as alkalis with a pKa of 12 or greater and less than 20, and ammonia(pKa: 9) and imidazole (pKa: 7) as alkalis with a pKa of less than 12.The pKa value of the alkali used is restricted by adjustment to anappropriate concentration, without being particularly limited thereto.

{Mixing Rate}

The absorbance for light with a wavelength of 400 nm or a wavelength of290 nm, and the light transmittance for light with a wavelength of 500nm, can be altered by controlling the mixing rate of the metal saltaqueous solution and the alkali solution. Specifically, the absorbancetends to be higher when the mixing rate is increased, while theabsorbance tends to be lower when the mixing rate is decreased. Also,the light transmittance for light with a wavelength of 500 nm tends tobe higher when the mixing rate is increased, while the lighttransmittance tends to be lower when the mixing rate is decreased.

From the viewpoint of absorbance and light transmittance, there is noparticular restriction on the lower limit for the mixing rate, but it ispreferably at least 0.1 ml/min from the viewpoint of shortening themixing time to increase efficiency. The upper limit for the mixing rateis preferably not greater than 100 ml/min, from the viewpoint ofminimizing rapid reaction. However, the mixing rate is preferablydetermined according to the starting concentrations, and specifically,the mixing rate is preferably decreased when the starting concentrationsare high, for example.

{Stirring Speed}

By controlling the stirring speed for mixing of the metal salt aqueoussolution and the alkali solution, it is possible to alter the lighttransmittance for light with a wavelength of 500 nm. Specifically, thelight transmittance tends to be higher when the stirring speed isincreased, while the light transmittance tends to be lower when thestirring speed is decreased.

As the stirring speed, for example, in the case of a mixing scale inwhich a stirring blade with a total length of 5 cm is used for stirringof a 2 L solution, the rotational speed of the stirring blade ispreferably 50-1000 rpm. The upper limit for the rotational speed ispreferably not greater than 1000 rpm, more preferably not greater than800 rpm and even more preferably not greater than 500 rpm, from theviewpoint of preventing excessive increase in the liquid level. In thecase of modifying (for example, enlarging) the mixing scale, the optimalstirring speed will be changed, but so long as it is within the range ofabout 50-1000 rpm, it is possible to obtain a polishing liquid withsatisfactory light transmittance.

{Liquid Temperature (Synthesis Temperature)}

By controlling the liquid temperature for mixing of the metal saltaqueous solution and the alkali solution, it is possible to alter thelight transmittance for light with a wavelength of 500 nm. Specifically,the light transmittance tends to be higher when the liquid temperatureis reduced, while the light transmittance tends to be lower when theliquid temperature is increased.

The liquid temperature is preferably within the range of 0-60° C., asthe temperature in the reaction system read upon placing a thermometerin the reaction system. The upper limit for the liquid temperature ispreferably not higher than 60° C., more preferably not higher than 50°C., even more preferably not higher than 40° C., especially preferablynot higher than 30° C. and especially preferably not higher than 25° C.,from the viewpoint of preventing rapid reaction. From the viewpoint offacilitating progression of the reaction, the lower limit for the liquidtemperature is preferably 0° C. or higher, more preferably 5° C. orhigher, even more preferably 10° C. or higher, especially morepreferably 15° C. or higher and extremely preferably 20° C. or higher.

The tetravalent metal element salt in the metal salt aqueous solutionand the base of the alkali solution are preferably reacted at a fixedsynthesis temperature T (for example, in a temperature range ofsynthesis temperature T±3° C.). The method of adjusting the synthesistemperature is not particularly restricted, and for example, it may be amethod in which a container holding either the metal salt aqueoussolution or the alkali solution is placed in a water tank filled withwater, and the metal salt aqueous solution and alkali solution are mixedwhile adjusting the water temperature of the water tank using a CoolnicsCirculator (product name: Cooling Thermopump CTP101 by Eyela) as theexternal circulation apparatus.

The tetravalent metal element hydroxide prepared as described above mayinclude impurities, but the impurities can be removed, for example, by amethod of repeating solid-liquid separation by centrifugal separation orthe like. This can adjust the absorbance for light with a wavelength of450-600 nm.

(Additives)

The polishing liquid of this embodiment is suitable for use in polishingof substrates with inorganic insulating films because it allows anespecially superior polishing rate to be obtained for inorganicinsulating films (for example, silicon oxide films), but appropriateselection of additives will allow high levels to be achieved for boththe polishing rate and the polishing properties other than polishingrate.

An additive used may be a known additive without any particularrestrictions, such as a dispersing agent that increases thedispersibility of the abrasive grains, a polishing rate improver thatimproves the polishing rate, a flattening agent (a flattening agent thatreduces irregularities on the polished surface after polishing, or aglobal flattening agent that improves the global flatness of thesubstrate after polishing), or a selection ratio improver that improvesthe polishing selective ratio of the inorganic insulating film withrespect to stopper films such as silicon nitride films or polysiliconfilms.

Examples of dispersing agents include vinyl alcohol polymers and theirderivatives, betaine, lauryl betaine, lauryldimethylamine oxide, and thelike. Examples of polishing rate improvers include β-alanine betaine,stearyl betaine, and the like. Examples of flattening agents that reduceirregularities on polished surfaces include ammonium lauryl sulfate,triethanolamine polyoxyethylene alkyl ether sulfate, and the like.Examples of global flattening agents include polyvinylpyrrolidone,polyacrolein, and the like. Examples of selection ratio improversinclude polyethyleneimine, polyallylamine, chitosan, and the like. Thesemay be used alone or in combinations of two or more.

The polishing liquid of this embodiment preferably comprises a vinylalcohol polymer or a derivative thereof as an additive. However, vinylalcohol, which is a monomer of polyvinyl alcohol, generally tends not toexist alone as stable compounds. Therefore, polyvinyl alcohol is usuallyobtained by polymerization of a vinyl carboxylate monomer such as vinylacetate monomer to obtain poly(vinyl carboxylate), followed bysaponification (hydrolysis). Thus, a vinyl alcohol polymer obtainedusing vinyl acetate monomer as the starting material, for example, has—OCOCH₃ and hydrolyzed —OH groups as functional groups in the molecule,and the proportion of —OH groups is defined as the saponificationdegree. That is, a vinyl alcohol polymer whose saponification degree isnot 100% has a structure which is essentially a copolymer of vinylacetate and vinyl alcohol. It may also be one in which a vinylcarboxylate monomer such as vinyl acetate monomer and another vinylgroup-containing monomer (for example, ethylene, propylene, styrene orvinyl chloride) are copolymerized, and all or some of the portionsderived from the vinyl carboxylate monomer are saponified. In theinvention, all of these are collectively referred to as “vinyl alcoholpolymers”, and a “vinyl alcohol polymer” is ideally a polymer having thefollowing structural formula.

(wherein n represents a positive integer)

A “derivative” of a vinyl alcohol polymer is defined as a term includinga derivative of a homopolymer of vinyl alcohol (that is, a polymer witha saponification degree of 100%), and derivatives of copolymers of vinylalcohol monomer and other vinyl group-containing monomers (for example,ethylene, propylene, styrene, vinyl chloride or the like).

Examples of the aforementioned derivatives include polymers having aportion of the hydroxyl groups substituted with amino, carboxyl, estergroups or the like, and polymers having a portion of the hydroxyl groupsmodified. Examples of such derivatives include reactive polyvinylalcohols (for example, GOHSEFIMER (registered trademark) Z by NipponSynthetic Chemical Industry Co., Ltd.), cationized polyvinyl alcohols(for example, GOHSEFIMER (registered trademark) K by Nippon SyntheticChemical Industry Co., Ltd.), anionized polyvinyl alcohols (for example,GOHSERAN (registered trademark) L and GOHSENOL (registered trademark) Tby Nippon Synthetic Chemical Industry Co., Ltd.), and hydrophilicgroup-modified polyvinyl alcohols (for example, ECOMATI by NipponSynthetic Chemical Industry Co., Ltd.).

As mentioned above, vinyl alcohol polymers and their derivativesfunction as abrasive grain dispersing agents, and have effects ofimproving polishing liquid stability. It is believed that interactionbetween the hydroxyl group of the vinyl alcohol polymer or itsderivative and tetravalent metal element hydroxide particles can inhibitaggregation of the abrasive grains and minimize changes in particle sizeof the abrasive grains in the polishing liquid, thereby improvingstability. Also, by using the vinyl alcohol polymer or its derivative incombination with tetravalent metal element hydroxide particles, it ispossible to increase the polishing selective ratio for inorganicinsulating films (for example, silicon oxide films) with respect tostopper films (for example, silicon nitride films and polysilicon films)(i.e., polishing rate for inorganic insulating films/polishing rate forstopper films). In addition, a vinyl alcohol polymer and its derivativecan also improve the flatness of the polished surface after polishing,and can prevent adhesion of abrasive grains on the polished surface(cleanability improver).

The saponification degree of the vinyl alcohol polymer is preferably notgreater than 95 mol % from the viewpoint of further increasing thepolishing selective ratio for inorganic insulating films with respect tostopper films. From the same viewpoint, the saponification degree ismore preferably not greater than 90 mol %, even more preferably notgreater than 88 mol %, especially preferably not greater than 85 mol %,extremely preferably not greater than 83 mol % and very preferably notgreater than 80 mol %.

There are no particular restrictions on the lower limit for thesaponification degree, but from the viewpoint of excellent solubility inwater, it is preferably at least 50 mol %, more preferably at least 60mol % and even more preferably at least 70 mol %. The saponificationdegree of the vinyl alcohol polymer can be measured according to JIS K6726 (Polyvinyl alcohol test method).

There are no particular restrictions on the upper limit for the meanpolymerization degree (weight-average molecular weight) of the vinylalcohol polymer, but from the viewpoint of further inhibiting reductionin polishing rate for inorganic insulating films (for example, siliconoxide films), it is preferably not greater than 3000, more preferablynot greater than 2000 and even more preferably not greater than 1000.

From the viewpoint of further increasing the polishing selective ratiofor inorganic insulating films with respect to stopper films, the lowerlimit for the mean polymerization degree is preferably at least 50, morepreferably at least 100 and even more preferably at least 150. The meanpolymerization degree of the vinyl alcohol polymer can be measuredaccording to JIS K 6726 (Polyvinyl alcohol test method).

In order to adjust the polishing selective ratio for inorganicinsulating films with respect to stopper films, and the flatness ofpolished substrates, a combination of multiple polymers with differentsaponification degrees or mean polymerization degrees may be used as thevinyl alcohol polymer or its derivative. In such cases, preferably thesaponification degree of at least one vinyl alcohol polymer and itsderivative is not greater than 95 mol %, and from the viewpoint offurther improving the polishing selective ratio, the averagesaponification degree calculated from each saponification degree and themixing ratio is preferably not greater than 95 mol %. The preferredrange for these saponification degrees is the same range specifiedabove.

From the viewpoint of more efficiently obtaining the effects ofadditives, the additive content is preferably 0.01 mass % or greater,more preferably 0.1 mass % or greater and even more preferably 1.0 mass% or greater, based on the total mass of the polishing liquid. From theviewpoint of further inhibiting reduction in the polishing rate forinorganic insulating films, the additive content is preferably notgreater than 10 mass %, more preferably not greater than 5.0 mass % andeven more preferably not greater than 3.0 mass % based on the total massof the polishing liquid.

(Water)

There are no particular restrictions on the water used in the polishingliquid of this embodiment, but deionized water or ultrapure water ispreferred. The water content is not particularly restricted and may bethe remaining portion of the polishing liquid excluding the otherconstituent components.

The method of dispersing the abrasive grains in water is notparticularly restricted, and specifically, a dispersion method employingstirring, a homogenizer, an ultrasonic disperser or a wet ball mill maybe used.

[Polishing Liquid Properties]

The pH of the polishing liquid is preferably 2.0-9.0, for a satisfactoryrelationship of the surface potential of the abrasive grains withrespect to the surface potential of the surface to be polished, tofacilitate action of the abrasive grains on the surface to be polished,and thereby obtaining a more superior polishing rate. From the viewpointof stabilizing the pH of the polishing liquid and minimizing problemssuch as aggregation of the abrasive grains due to addition of a pHstabilizer, the lower limit for the pH is preferably at least 2.0, morepreferably at least 4.0 and even more preferably at least 5.0. Also,from the viewpoint of excellent dispersibility of the abrasive grainsand obtaining a more superior polishing rate, the upper limit for the pHis preferably not greater than 9.0, more preferably not greater than 7.5and even more preferably not greater than 6.5.

The pH of the polishing liquid can be measured with a pH meter (forexample, a Model PH81 by Yokogawa Electric Corp.).

The pH is measured by placing an electrode in the polishing liquid after2-point calibration using standard buffer (phthalate pH buffer: pH 4.01(25° C.), neutral phosphate pH buffer: pH 6.86 (25° C.)), and thenmeasuring the value upon stabilization after an elapse of 2 minutes ormore.

Any known pH regulator may be used to adjust the pH of the polishingliquid, without any particular restrictions, and specifically, there maybe used inorganic acids such as phosphoric acid, sulfuric acid or nitricacid, organic acids such as formic acid, acetic acid, propionic acid,maleic acid, phthalic acid, citric acid or succinic acid, amines such asethylenediamine, toluidine, piperazine, histidine or aniline, andnitrogen-containing heterocyclic compounds such as pyridine, imidazole,triazole or pyrazole.

A pH stabilizer is an additive for adjustment to a prescribed pH, and itis preferably a buffer component. The buffer component is preferably acompound with a pKa in the range of ±1.5, and more preferably a compoundwith a pKa in the range of ±1.0, relative to the prescribed pH. Suchcompounds include amino acids such as glycine, arginine, lysine,asparagine, aspartic acid and glutamic acid, amines such asethylenediamine, 2-aminopyridine, 3-aminopyridine, picolinic acid,histidine, piperazine, morpholine, piperidine, hydroxylamine andaniline, nitrogen-containing heterocyclic compounds such as pyridine,imidazole, benzimidazole, pyrazole, triazole and benzotriazole, andcarboxylic acids such as formic acid, acetic acid, propionic acid,malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid,fumaric acid, phthalic acid, citric acid, lactic acid and benzoic acid.

<Slurry>

The slurry of this embodiment may be used directly for polishing, or itmay be used as a slurry in a “two-pack type polishing liquid”, havingthe constituent components of the polishing liquid separated into aslurry and an additive solution. According to this embodiment, thepolishing liquid and the slurry differ in the presence or absence ofadditives, and the polishing liquid is obtained by adding the additivesto the slurry.

The slurry of this embodiment comprises at least the same abrasivegrains as the polishing liquid of this embodiment, and water. Forexample, the abrasive grains include a tetravalent metal elementhydroxide, and produce a liquid phase with a nonvolatile content of 500ppm or greater when an aqueous dispersion with a content of the abrasivegrains adjusted to 1.0 mass % has been centrifuged for 50 minutes at acentrifugal acceleration of 1.59×10⁵ G. The mean secondary particle sizeof the abrasive grains is the same as the abrasive grains used in thepolishing liquid of this embodiment. These preferred ranges andmeasuring methods for the nonvolatile content and mean secondaryparticle size are the same as for the polishing liquid of thisembodiment.

In the slurry of this embodiment, the abrasive grains preferably satisfyat least one of conditions (a) and (b) above. Also, the abrasive grainspreferably produce absorbance of not greater than 0.010 for light with awavelength of 450-600 nm in an aqueous dispersion with a content of theabrasive grains adjusted to 0.0065 mass %. Also, the abrasive grainspreferably produce light transmittance of 50%/cm or greater for lightwith a wavelength of 500 nm in an aqueous dispersion with a content ofthe abrasive grains adjusted to 1.0 mass %. These preferred ranges andmeasuring methods for the absorbance and light transmittance are thesame as for the polishing liquid of this embodiment.

In the slurry of this embodiment, the abrasive grain content is notparticularly restricted, but it is preferably not greater than 15 mass %based on the total mass of the slurry, from the viewpoint of helping toavoid aggregation of the abrasive grains. The abrasive grain content ispreferably 0.01 mass % or greater based on the total mass of the slurry,from the viewpoint of allowing the mechanical effect of the abrasivegrains to be easily obtained.

Of the constituent components of the slurry of this embodiment, thetetravalent metal element hydroxide is believed to have a major effecton the polishing properties. The tetravalent metal element hydroxidecontent is preferably not greater than 10 mass % based on the total massof the slurry, from the viewpoint of helping to avoid aggregation of theabrasive grains, as well as achieving satisfactory chemical interactionwith the surface to be polished and thereby allowing further improvementin the polishing rate. The tetravalent metal element hydroxide contentis preferably 0.01 mass % or greater based on the total mass of theslurry, from the viewpoint of allowing the function of the tetravalentmetal element hydroxide to be adequately exhibited.

The pH of the slurry of this embodiment is preferably 2.0-9.0, for asatisfactory surface potential of the abrasive grains with respect tothe surface potential of the surface to be polished, to facilitateaction of the abrasive grains on the surface to be polished, and therebyobtaining a more superior polishing rate. Also, from the viewpoint ofstabilizing the pH of the slurry and minimizing problems such asaggregation of the abrasive grains due to addition of a pH stabilizer,the lower limit for the pH is preferably at least 2.0, more preferablyat least 2.5 and even more preferably at least 3.0. Furthermore, fromthe viewpoint of excellent dispersibility of the abrasive grains andobtaining a more superior polishing rate, the upper limit for the pH ispreferably not greater than 9.0, more preferably not greater than 7.0and even more preferably not greater than 5.0. The pH of the slurry canbe measured by the same method as for the pH of the polishing liquid ofthis embodiment.

<Polishing Liquid Set>

In the polishing liquid set of this embodiment, the constituentcomponents of the polishing liquid are separately stored as a slurry andan additive solution, so that the slurry (first liquid) and additivesolution (second liquid) are mixed to form the polishing liquid. Theslurry used may be the slurry according to this embodiment. The additivesolution used may be a solution having the additive dissolved in water.The polishing liquid set is used as a polishing liquid by mixing theslurry and additive solution at the time of polishing. By thusseparately storing the constituent components of the polishing liquidinto at least two liquids, it is possible to obtain a polishing liquidwith excellent storage stability.

The additives used in the additive solution may be the same additives asdescribed for the polishing liquid. The content of additives in theadditive solution is preferably 0.01-20 mass % and more preferably0.02-20 mass %, based on the total mass of the additive solution, fromthe viewpoint of inhibiting excessive reduction in the polishing ratewhen the additive solution and slurry are mixed to form the polishingliquid.

There are no particular restrictions on the water for the additivesolution, but deionized water or ultrapure water is preferred. The watercontent is not particularly restricted and may be the content of theremainder excluding the other constituent components.

<Substrate Polishing Method and Substrate>

A substrate polishing method using the aforementioned polishing liquid,slurry or polishing liquid set, and a substrate obtained by the method,will now be described. When the polishing liquid or slurry is to beused, it will be a polishing method using a one-pack type polishingliquid, and when the polishing liquid set is to be used, it will be apolishing method using a two-pack type polishing liquid or a three-packor greater type polishing liquid.

In the substrate polishing method of this embodiment, polishing isperformed on a substrate having a film to be polished on its surface. Inthe substrate polishing method of this embodiment, the film to bepolished may be polished using a stopper film formed under the film tobe polished. The substrate polishing method of this embodiment comprisesat least a substrate positioning step and a polishing step. In thesubstrate positioning step, a film to be polished, of a substrate whichhas the film to be polished on its surface, is placed so as to face anabrasive pad.

The film to be polished is preferably an inorganic insulating film, suchas a silicon oxide film. The silicon oxide film can be obtained bylow-pressure CVD method, plasma CVD, or the like. The silicon oxide filmmay be doped with an element such as phosphorus or boron. The inorganicinsulating film may be a Low-k film or the like. The surface of the filmto be polished (surface to be polished) preferably has irregularities.In the substrate polishing method of this embodiment, the convexities ofthe irregularities of the film to be polished are preferentiallypolished, to obtain a substrate with a flattened surface.

In the polishing step, when a one-pack type polishing liquid is to beused, in the state that the film to be polished of the substrate ispressed against the abrasive pad of the polishing platen, at least aportion of the film to be polished is polished by relatively moving thesubstrate and the polishing platen while supplying the polishing liquidor slurry between the abrasive pad and the film to be polished. Here,the polishing liquid and slurry may be supplied onto the abrasive paddirectly as a polishing liquid with the prescribed water content.

From the viewpoint of minimizing costs for preservation, transport andstorage, the polishing liquid and slurry of this embodiment can bestored as a storage solution for a polishing liquid or a storagesolution for a slurry to be used, for example, in a two-fold or greaterdilution with a liquid medium such as water at the time of use. Thestorage solution may be diluted with the liquid medium immediatelybefore polishing, or the storage solution and liquid medium may besupplied onto the abrasive pad for dilution on the abrasive pad.

Since a greater dilution factor of the storage solution results in agreater effect of minimizing cost for preservation, transport andstorage, it is preferably two-fold or greater and more preferably 3-foldor greater. There are no particular restrictions on the upper limit, buta greater dilution factor requires a greater amount of components in thestorage solution (a higher concentration), which tend to lower thestability during storage, and therefore it is preferably not greaterthan 500-fold, more preferably not greater than 200-fold, even morepreferably not greater than 100-fold and especially preferably notgreater than 50-fold. The same is applied for a polishing liquid withthe constituent components divided into 3 or more liquids.

When a two-pack type polishing liquid is to be used, the method mayinclude a polishing liquid preparation step in which the slurry andadditive solution are mixed before the polishing step to obtain apolishing liquid. In this case, in the polishing step, the film to bepolished is polished using the polishing liquid obtained from thepolishing liquid preparation step. In the polishing liquid preparationstep of this polishing method, the slurry and additive solution areconveyed through separate tubings, and the tubings are merged justbefore the supply tubing outlet to obtain the polishing liquid.Alternatively, the polishing liquid may be supplied onto the abrasivepad directly as a polishing liquid with the prescribed water content.The same is applied for a polishing liquid with the constituentcomponents divided into 3 or more liquids.

In the polishing step, when a two-pack type of polishing liquid is to beused, at least a portion of the film to be polished may be polishedusing the polishing liquid obtained by mixing the slurry and additivesolution while respectively supplying the slurry and additive solution.In this polishing method, the slurry and additive solution may besupplied onto the abrasive pad through separate liquid conveyancesystems. The slurry may be diluted on the abrasive pad after beingsupplied onto the abrasive pad as the aforementioned slurry storagesolution, and the additive solution may be diluted on the abrasive padafter being supplied onto the abrasive pad as a storage solution with alow water content. The same is applied for a polishing liquid with theconstituent components divided into 3 or more liquids.

The polishing apparatus to be used in the polishing method of thisembodiment may be, for example, a common polishing apparatus comprisinga holder to hold the substrate with the film to be polished, and apolishing platen that mounts a motor having a variable rotational speedand allows attachment of an abrasive pad. Examples of such polishingapparatuses include a polishing apparatus by Ebara Corp. (ModelEPO-111), and polishing apparatuses by Applied Materials (trade names:Mirra3400 and Reflection Polishing Machine).

There are no particular restrictions on the abrasive pad, and a commonnonwoven fabric, foamed polyurethane, porous fluorine resin or the likemay be used. The abrasive pad is preferably furrowed to allowaccumulation of the polishing liquid.

The polishing conditions are not particularly restricted, but from theviewpoint of minimizing fly off of the semiconductor substrate, therotational speed of the polishing platen is preferably a low speed ofnot greater than 200 rpm. The pressure (machining load) on thesemiconductor substrate is preferably not greater than 100 kPa, from theviewpoint of further minimizing formation of scratches after polishing.The polishing liquid is preferably continuously supplied to the surfaceof the abrasive pad with a pump or the like during polishing. The amountsupplied is not particularly restricted, but the surface of the abrasivepad is preferably covered by the polishing liquid at all times.Preferably, the polished semiconductor substrate is thoroughly rinsed inrunning water, and is then dried after removing off the water dropletsadhering to the semiconductor substrate using a spin dryer or the like.

According to this embodiment, there is provided the use of theaforementioned polishing liquid, slurry and polishing liquid set forpolishing of a film to be polished (for example, a silicon oxide film).Also according to this embodiment, there is provided the use of theaforementioned polishing liquid, slurry and polishing liquid set forpolishing of a film to be polished (for example, a silicon oxide film)using a stopper film (for example, a silicon nitride film or polysiliconfilm).

EXAMPLES

The present invention will now be described in greater detail byexamples, with the understanding that the invention is not limited tothese examples.

Examples 1 to 6, Comparative Examples 1 and 2 Preparation of TetravalentMetal Element Hydroxides

Tetravalent metal element hydroxides were prepared by the followingprocedure. The values indicated as A to G throughout the explanationbelow are the values shown in Table 1.

After placing A [g] of water into a container, B [g] of cerium ammoniumnitrate aqueous solution (general formula: Ce(NR)₂(NO₃)₆, formulaweight: 548.2 g/mol) at a concentration of 50 mass % was added and mixedtherewith, and the liquid temperature was adjusted to C [° C.] to obtaina metal salt aqueous solution. The metal salt concentration of the metalsalt aqueous solution was as shown in Table 1.

Next, the alkali shown in Table 1 was dissolved in water to prepare E[g] of an aqueous solution at a concentration of D [mol/L], and theliquid temperature was adjusted to a temperature of C [° C.] to obtainan alkali solution.

The container holding the metal salt aqueous solution was placed in awater tank filled with water and the water temperature of the water tankwas adjusted to the temperature indicated by C [° C.] in Table 1 usingan external-circulating Coolnics Circulator (product name: CoolingThermopump CTP101 by Eyela). The alkali solution was added into thecontainer at a mixing rate of G [mL/min] while keeping the watertemperature at C [° C.] and stirring the metal salt aqueous solution atthe stirring speed indicated by F [rpm] in Table 1, to obtain slurryprecursor 1 comprising abrasive grains of tetravalent cerium hydroxide.The pH of slurry precursor 1 was as indicated by “final pH” in Table 1.In Example 4, a 4-blade pitched paddle with a total blade length of 17cm was used for stirring of the metal salt aqueous solution, while inthe other examples and the comparative examples, an ordinary stirringblade with a total blade length of 5 cm was used for stirring of themetal salt aqueous solution.

Slurry precursor 1 was centrifuged and subjected to solid-liquidseparation by decantation to remove the liquid. The procedure of addinga suitable amount of water to the obtained resultant solid, thoroughlystirring and conducting solid-liquid separation by decantation wascarried out an additional 3 times.

After again adding water to the obtained resultant solid to adjust theliquid volume to 2.0 L, ultrasonic dispersion treatment was carried outfor 180 minutes to obtain slurry precursor 2. A suitable amount of theobtained slurry precursor 2 was sampled, and the mass after drying (thenonvolatile component mass) was measured to calculate the content oftetravalent cerium hydroxide abrasive grains in the slurry precursor 2.

TABLE 1 Metal salt solution Alkali solution 50 mass % Alkali Synthesisconditions Water metal salt so- solution Mixing Stirring Synthesisamount lution amount Concentration Concentration amount speed speedtemp. A [g] B [g] [mol/L] Alkali type D [mol/L] E [g] G [mL/min] F [rpm]C [° C.] Final pH Example 1 1840 76.8 0.037 Ammonia 8.8 29 10 200 25 5.2Example 2 1656 69.1 0.037 Imidazole 1.5 152 10 500 10 5.2 Example 3 165669.1 0.037 Imidazole 1.5 152 5 500 10 5.2 Example 4 165600 6912 0.037Imidazole 1.5 15200 80 100 15 5.2 Example 5 1656 69.1 0.037 Imidazole1.5 152 2 500 10 5.2 Example 6 1656 69.1 0.037 Imidazole 1.5 152 10 50025 4.5 Comp. Ex. 1 1840 76.8 0.037 Ammonia 14.7 17 25 200 25 5.2 Comp.Ex. 2 2500 40.0 0.014 Potassium 1.8 70 10 500 25 5.2 hydroxide

(Measurement of Nonvolatile Content of Supernatant Liquid afterCentrifugal Separation)

A suitable amount of slurry precursor 2 was sampled and diluted withwater to an abrasive grain content of 1.0 mass % to obtain a measuringsample (aqueous dispersion). The sample was filled into the centrifugetube of an ultracentrifuge by Hitachi Koki Co., Ltd. (apparatus name:70P-72), and the ultracentrifuge was used for 50 minutes ofcentrifugation at a rotational speed of 50000 (rpm). In theultracentrifuge, the tube angle was 26°, the minimum radius R_(min) was3.53 cm, the maximum radius R_(max) was 7.83 cm and the average radiusR_(av) was 5.68 cm. The centrifugal acceleration calculated from averageradius R_(av) was 158756 G=1.59×10⁵ G.

After sampling 5.0 g of the supernatant liquid from the tube aftercentrifugal separation, the dried mass was measured to calculate thenonvolatile content of the supernatant liquid (the content oftetravalent cerium hydroxide abrasive grains). The results are shown inTable 2.

(Measurement of Absorbance and Light Transmittance)

A suitable amount of slurry precursor 2 was sampled and diluted withwater to an abrasive grain content of 0.0065 mass % (65 ppm) to obtain ameasuring sample (aqueous dispersion). Approximately 4 mL of themeasuring sample was placed in a 1 cm-square cell, and the cell was setin a spectrophotometer (apparatus name: U3310) by Hitachi, Ltd.Spectrophotometry was performed in a wavelength range of 200-600 nm todetermine the absorbance at a wavelength of 290 nm and the absorbance ata wavelength of 450-600 nm. The results are shown in Table 2.

A suitable amount of slurry precursor 2 was also sampled and dilutedwith water to an abrasive grain content of 1.0 mass % to obtain ameasuring sample (aqueous dispersion). Approximately 4 mL of themeasuring sample was placed in a 1 cm-square cell, and the cell was setin a spectrophotometer (apparatus name: U3310) by Hitachi, Ltd.Spectrophotometry was performed in a wavelength range of 200-600 nm tomeasure the absorbance for light with a wavelength of 400 nm and thelight transmittance for light with a wavelength of 500 nm. The resultsare shown in Table 2.

(Measurement of Mean Secondary Particle Size)

A suitable amount of slurry precursor 2 was sampled and diluted withwater to an abrasive grain content of 0.2 mass % to obtain a measuringsample. Approximately 4 mL of the measuring sample was placed in a 1cm-square cell, and the cell was set in a Zetasizer 3000HS, an apparatusname by Malvern Instruments Ltd. Measurement was conducted at 25° C.with a dispersing medium refractive index of 1.33 and a viscosity of0.887 mPa·s, and the value represented by Z-average Size was read as themean secondary particle size. The results are shown in Table 2.

TABLE 2 Light Supernatant Absorbance Absorbance Absorbance transmittanceMean nonvolatile [290 nm] [450-600 nm] [400 nm] [500 nm] [%/cm]secondary content Abrasive grain content: Abrasive grain content:particle size [ppm] 65 ppm 1.0 mass % [nm] Example 1 760 1.112 <0.0101.57 62 74 Example 2 1280 1.140 <0.010 1.83 >99 21 Example 3 1830 1.238<0.010 2.28 >99 24 Example 4 3020 1.312 <0.010 3.02 >99 18 Example 52380 1.232 <0.010 2.68 >99 20 Example 6 3070 1.230 <0.010 2.04 >99 22Comp. Ex. 1 280 1.256 <0.010 2.70 41 95 Comp. Ex. 2 370 1.239 <0.0102.22 46 91

(Preparation of Polishing Liquids)

Water was added to slurry precursor 2 for adjustment to an abrasivegrain content of 1 mass % to obtain a storage solution for a slurry. Theresults of observing the outer appearance of each storage solution for aslurry are shown in Table 3.

Purified water was added to 60 g of the storage solution for a slurry toobtain a slurry. Also, a 5 mass % polyvinyl alcohol aqueous solution wasprepared as an additive solution. After adding 60 g of the additivesolution to the slurry, the mixture was mixed and stirred to obtain apolishing liquid with an abrasive grain content of 0.2 mass %. Theamount of purified water added was calculated to be for a final abrasivegrain content of 0.2 mass %. The saponification degree of polyvinylalcohol in the polyvinyl alcohol aqueous solution was 80 mol %, and themean polymerization degree was 300. The polyvinyl alcohol content in thepolishing liquid was 1.0 mass %. The pH (25° C.) values of the slurryand polishing liquid, as measured using a Model PH81 by YokogawaElectric Corp., were 3.6 and 6.0.

(Polishing of Insulating Film)

A φ200 mm silicon wafer, with a silicon oxide insulating film formedthereon, was set in the holder of a polishing apparatus, mounting anadsorption pad for substrate attachment. The holder was placed on aporous urethane resin pad-attached platen, with the insulating filmfacing the pad. The substrate was pressed onto the pad at a polishingload of 20 kPa while supplying the obtained polishing liquid onto thepad at a feed rate of 200 cc/min. Polishing was performed for 1 minuteof rotation of the platen at 78 rpm and the holder at 98 rpm. Thepolished wafer was thoroughly washed with purified water and dried. Alight-interference film thickness meter was used to measure the changein film thickness before and after polishing, and the polishing rate wascalculated. The results are shown in Table 3.

Evaluation of the absorbance, light transmittance and polishing ratewere all conducted within 24 hours after preparing slurry precursor 2.

FIG. 4 shows the relationship between nonvolatile content of thesupernatant liquid [ppm] and polishing rate, FIG. 5 shows therelationship between absorbance for light with a wavelength of 290 nmand polishing rate, and FIG. 6 shows the relationship between absorbancefor light with a wavelength of 400 nm and polishing rate. Also, therelationship between absorbance for light with a wavelength of 290 nmand absorbance for light with a wavelength of 400 nm is shown in FIG. 7.In FIGS. 5 to 7, a case with a light transmittance of 90%/cm or greateris indicated by a circle, a case with a light transmittance of at least50%/cm and less than 90%/cm is indicated by a triangle, and a case witha light transmittance of less than 50%/cm is indicated by a diamond.

As clearly seen in FIG. 4, a higher nonvolatile content of thesupernatant liquid is associated with improved polishing rate. Also, asclearly seen in FIGS. 5 to 6, for a polishing liquid with a highnonvolatile content of the supernatant liquid, higher absorbance forlight with a wavelength of 290 nm or higher absorbance for light with awavelength of 400 nm is associated with improved polishing rate. Also,FIG. 7 shows a good correlation between absorbance for light with awavelength of 290 nm and absorbance for light with a wavelength of 400nm.

TABLE 3 Outer appearance of Polishing rate storage solution for slurry(nm/min) Example 1 Slightly turbid, faint yellow 280 Example 2Transparent, faint yellow 350 Example 3 Transparent, faint yellow 377Example 4 Transparent, faint yellow 405 Example 5 Transparent, faintyellow 389 Example 6 Transparent, faint yellow 376 Comp. Ex. 1 Turbid,white 170 Comp. Ex. 2 Turbid, white 190

Next, using a polishing liquid obtained using the slurry of Example 2and a polishing liquid obtained using the slurry of Comparative Example1, the relationship between polyvinyl alcohol (PVA) content of thepolishing liquid and polishing rate was examined. Specifically, thepolishing rates for silicon oxide films were examined in the same manneras Example 1, with polyvinyl alcohol contents of 3.0 mass %, 2.0 mass %,1.0 mass %, 0.5 mass % and 0.1 mass % in the polishing liquid. Theresults are shown in Table 4.

TABLE 4 PVA content (mass %) 3.0 2.0 1.0 0.5 0.1 Polishing Comp. Ex. 190 135 170 225 232 rate Example 2 253 312 350 375 384 (nm/min)

As is clear by the results in Table 4, the polishing rate in Example 2,which employed abrasive grains that produce a liquid phase with anonvolatile content of 500 ppm or greater, was higher than inComparative Example 1 with addition of additives in the same amount, andtherefore a wide margin exists for further addition of additives, inaddition to polyvinyl alcohol. It is thought that the polishing rate wasimproved by the increased proportion of fine particles accompanying thehigher nonvolatile content, and thus by the increased surface area ofabrasive grains contacting with the surface to be polished. Thisindicates that in Example 2 it is possible to impart further propertiesby adding more additives, compared to Comparative Example 1.

REFERENCE SIGNS LIST

1: Angle rotor, A1: rotation axis, A2: tube angle, R_(min): minimumradius, R_(max): maximum radius, R_(av): average radius.

1. A slurry comprising abrasive grains and water, the abrasive grainsincluding a tetravalent metal element hydroxide, and producing a liquidphase with a nonvolatile content of 500 ppm or greater when an aqueousdispersion with a content of the abrasive grains adjusted to 1.0 mass %has been centrifuged for 50 minutes at a centrifugal acceleration of1.59×10⁵ G, wherein the abrasive grains produce absorbance of at least1.50 for light with a wavelength of 400 nm in an aqueous dispersion witha content of the abrasive grains adjusted to 1.0 mass %.
 2. (canceled)3. The slurry according to claim 1, wherein the abrasive grains produceabsorbance of at least 1.000 for light with a wavelength of 290 nm in anaqueous dispersion with a content of the abrasive grains adjusted to0.0065 mass %.
 4. The slurry according to claim 1, wherein the abrasivegrains produce absorbance of not greater than 0.010 for light with awavelength of 450-600 nm in an aqueous dispersion with a content of theabrasive grains adjusted to 0.0065 mass %.
 5. The slurry according toclaim 1, wherein the abrasive grains produce light transmittance of50%/cm or greater for light with a wavelength of 500 nm in an aqueousdispersion with a content of the abrasive grains adjusted to 1.0 mass %.6. The slurry according to claim 1, wherein the tetravalent metalelement hydroxide is obtained by mixing a tetravalent metal element saltand an alkali solution.
 7. The slurry according to claim 1, wherein thetetravalent metal element is tetravalent cerium.
 8. A polishing liquidset comprising constituent components of a polishing liquid separatelystored as a first liquid and a second liquid, so that the first liquidand second liquid are mixed to form the polishing liquid, wherein thefirst liquid is the slurry according to claim 1, and the second liquidcomprises an additive and water.
 9. The polishing liquid set accordingto claim 8, wherein the additive is at least one selected from the groupconsisting of vinyl alcohol polymers and derivatives of the vinylalcohol polymers.
 10. The polishing liquid set according to claim 8,wherein a content of the additive is 0.01 mass % or greater based on atotal mass of the polishing liquid.
 11. A polishing liquid comprisingabrasive grains, an additive and water, the abrasive grains including atetravalent metal element hydroxide, and producing a liquid phase with anonvolatile content of 500 ppm or greater when an aqueous dispersionwith a content of the abrasive grains adjusted to 1.0 mass % has beencentrifuged for 50 minutes at a centrifugal acceleration of 1.59×10⁵ G,and wherein the abrasive grains produce absorbance of at least 1.50 forlight with a wavelength of 400 nm in an aqueous dispersion with acontent of the abrasive grains adjusted to 1.0 mass %.
 12. (canceled)13. The polishing liquid according to claim 11, wherein the abrasivegrains produce absorbance of at least 1.000 for light with a wavelengthof 290 nm in an aqueous dispersion with a content of the abrasive grainsadjusted to 0.0065 mass %.
 14. The polishing liquid according to claim11, wherein the abrasive grains produce absorbance of not greater than0.010 for light with a wavelength of 450-600 nm in an aqueous dispersionwith a content of the abrasive grains adjusted to 0.0065 mass %.
 15. Thepolishing liquid according to claim 11, wherein the abrasive grainsproduce light transmittance of 50%/cm or greater for light with awavelength of 500 nm in an aqueous dispersion with a content of theabrasive grains adjusted to 1.0 mass %.
 16. The polishing liquidaccording to claim 11, wherein the tetravalent metal element hydroxideis obtained by mixing a tetravalent metal element salt and an alkalisolution.
 17. The polishing liquid according to claim 11, wherein thetetravalent metal element is tetravalent cerium.
 18. The polishingliquid according to claim 11, wherein the additive is at least oneselected from the group consisting of vinyl alcohol polymers andderivatives of the vinyl alcohol polymers.
 19. The polishing liquidaccording to claim 11, wherein a content of the additive is 0.01 mass %or greater based on a total mass of the polishing liquid.
 20. Asubstrate polishing method comprising: a step of placing a film to bepolished, of a substrate which has the film to be polished on itssurface, so as to face an abrasive pad, and a step of polishing at leasta portion of the film to be polished while supplying the slurryaccording to claim 1 between the abrasive pad and the film to bepolished.
 21. A substrate polishing method comprising: a step of placinga film to be polished, of a substrate which has the film to be polishedon its surface, so as to face an abrasive pad, a step of mixing thefirst liquid and second liquid of the polishing liquid set according toclaim 8 to obtain the polishing liquid, and a step of polishing at leasta portion of the film to be polished while supplying the polishingliquid between the abrasive pad and the film to be polished.
 22. Asubstrate polishing method comprising: a step of placing a film to bepolished, of a substrate which has the film to be polished on itssurface, so as to face an abrasive pad, and a step of polishing at leasta portion of the film to be polished while respectively supplying boththe first liquid and second liquid of the polishing liquid set accordingto claim 8 between the abrasive pad and the film to be polished.
 23. Asubstrate polishing method comprising: a step of placing a film to bepolished, of a substrate which has the film to be polished on itssurface, so as to face an abrasive pad, and a step of polishing at leasta portion of the film to be polished while supplying the polishingliquid according to claim 11 between the abrasive pad and the film to bepolished.
 24. The polishing method according to claim 20, wherein thefilm to be polished includes silicon oxide.
 25. The polishing methodaccording to claim 20, wherein a surface of the film to be polished hasirregularities.
 26. (canceled)
 27. The polishing method according toclaim 21, wherein the film to be polished includes silicon oxide. 28.The polishing method according to claim 22, wherein the film to bepolished includes silicon oxide.
 29. The polishing method according toclaim 23, wherein the film to be polished includes silicon oxide. 30.The polishing method according to claim 21, wherein a surface of thefilm to be polished has irregularities.
 31. The polishing methodaccording to claim 22, wherein a surface of the film to be polished hasirregularities.
 32. The polishing method according to claim 23, whereina surface of the film to be polished has irregularities.
 33. A slurrycomprising abrasive grains and water, the abrasive grains including atetravalent metal element hydroxide, and producing a liquid phase with anonvolatile content of 500 ppm or greater when an aqueous dispersionwith a content of the abrasive grains adjusted to 1.0 mass % has beencentrifuged for 50 minutes at a centrifugal acceleration of 1.59×10⁵ G,the abrasive grains producing absorbance of at least 1.000 for lightwith a wavelength of 290 nm in an aqueous dispersion with a content ofthe abrasive grains adjusted to 0.0065 mass %.
 34. The slurry accordingto claim 33, wherein the abrasive grains produce absorbance of notgreater than 0.010 for light with a wavelength of 450-600 nm in anaqueous dispersion with a content of the abrasive grains adjusted to0.0065 mass %.
 35. The slurry according to claim 33, wherein theabrasive grains produce light transmittance of 50%/cm or greater forlight with a wavelength of 500 nm in an aqueous dispersion with acontent of the abrasive grains adjusted to 1.0 mass %.
 36. The slurryaccording to claim 33, wherein the tetravalent metal element hydroxideis obtained by mixing a tetravalent metal element salt and an alkalisolution.
 37. The slurry according to claim 33, wherein the tetravalentmetal element is tetravalent cerium.
 38. A polishing liquid setcomprising constituent components of a polishing liquid separatelystored as a first liquid and a second liquid, so that the first liquidand second liquid are mixed to form the polishing liquid, wherein thefirst liquid is the slurry according to claim 33, and the second liquidcomprises an additive and water.
 39. The polishing liquid set accordingto claim 38, wherein the additive is at least one selected from thegroup consisting of vinyl alcohol polymers and derivatives of the vinylalcohol polymers.
 40. The polishing liquid set according to claim 38,wherein a content of the additive is 0.01 mass % or greater based on atotal mass of the polishing liquid.
 41. A polishing liquid comprisingabrasive grains, an additive and water, the abrasive grains including atetravalent metal element hydroxide, and producing a liquid phase with anonvolatile content of 500 ppm or greater when an aqueous dispersionwith a content of the abrasive grains adjusted to 1.0 mass % has beencentrifuged for 50 minutes at a centrifugal acceleration of 1.59×10⁵ G,the abrasive grains producing absorbance of at least 1,000 for lightwith a wavelength of 290 nm in an aqueous dispersion with a content ofthe abrasive grains adjusted to 0.0065 mass %.
 42. The polishing liquidaccording to claim 41, wherein the abrasive grains produce absorbance ofnot greater than 0.010 for light with a wavelength of 450-600 nm in anaqueous dispersion with a content of the abrasive grains adjusted to0.0065 mass %.
 43. The polishing liquid according to claim 41, whereinthe abrasive grains produce light transmittance of 50%/cm or greater forlight with a wavelength of 500 nm in an aqueous dispersion with acontent of the abrasive grains adjusted to 1.0 mass %.
 44. The polishingliquid according to claim 41, wherein the tetravalent metal elementhydroxide is obtained by mixing a tetravalent metal element salt and analkali solution.
 45. The polishing liquid according to claim 41, whereinthe tetravalent metal element is tetravalent cerium.
 46. The polishingliquid according to claim 41, wherein the additive is at least oneselected from the group consisting of vinyl alcohol polymers andderivatives of the vinyl alcohol polymers.
 47. The polishing liquidaccording to claim 41, wherein a content of the additive is 0.01 mass %or greater based on a total mass of the polishing liquid.
 48. Asubstrate polishing method comprising: a step of placing a film to bepolished, of a substrate which has the film to be polished on itssurface, so as to face an abrasive pad, and a step of polishing at leasta portion of the film to be polished while supplying the slurryaccording to claim 33 between the abrasive pad and the film to bepolished.
 49. A substrate polishing method comprising: a step of placinga film to be polished, of a substrate which has the film to be polishedon its surface, so as to face an abrasive pad, a step of mixing thefirst liquid and second liquid of the polishing liquid set to claim 38to obtain the polishing liquid, and a step of polishing at least aportion of the film to be polished while supplying the polishing liquidbetween the abrasive pad and the film to be polished.
 50. A substratepolishing method comprising: a step of placing a film to be polished, ofa substrate which has the film to be polished on its surface, so as toface an abrasive pad, and a step of polishing at least a portion of thefilm to be polished while respectively supplying both the first liquidand second liquid of the polishing liquid set according to claim 38between the abrasive pad and the film to be polished.
 51. A substratepolishing method comprising: a step of placing a film to be polished, ofa substrate which has the film to be polished on its surface, so as toface an abrasive pad, and a step of polishing at least a portion of thefilm to be polished while supplying the polishing liquid according toclaim 41 between the abrasive pad and the film to be polished.
 52. Thepolishing method according to claim 48, wherein the film to be polishedincludes silicon oxide.
 53. The polishing method according to claim 49,wherein the film to be polished includes silicon oxide.
 54. Thepolishing method according to claim 50, wherein the film to be polishedincludes silicon oxide.
 55. The polishing method according to claim 51,wherein the film to be polished includes silicon oxide.
 56. Thepolishing method according to claim 48, wherein a surface of the film tobe polished has irregularities.
 57. The polishing method according toclaim 49, wherein a surface of the film to be polished hasirregularities.
 58. The polishing method according to claim 50, whereina surface of the film to be polished has irregularities.
 59. Thepolishing method according to claim 51, wherein a surface of the film tobe polished has irregularities.
 60. A slurry comprising abrasive grainsand water, the abrasive grains including a tetravalent metal elementhydroxide, and producing a liquid phase with a nonvolatile content of500 ppm or greater when an aqueous dispersion with a content of theabrasive grains adjusted to 1.0 mass % has been centrifuged for 50minutes at a centrifugal acceleration of 1.59×10⁵ G, the abrasive grainsproducing absorbance of not greater than 0.010 for light with awavelength of 450-600 nm in an aqueous dispersion with a content of theabrasive grains adjusted to 0.0065 mass %.
 61. The slurry according toclaim 60, wherein the abrasive grains produce light transmittance of50%/cm or greater for light with a wavelength of 500 nm in an aqueousdispersion with a content of the abrasive grains adjusted to 1.0 mass %.62. The slurry according to claim 60, wherein the tetravalent metalelement hydroxide is obtained by mixing a tetravalent metal element saltand an alkali solution.
 63. The slurry according to claim 60, whereinthe tetravalent metal element is tetravalent cerium.
 64. A polishingliquid set comprising constituent components of a polishing liquidseparately stored as a first liquid and a second liquid, so that thefirst liquid and second liquid are mixed to form the polishing liquid,wherein the first liquid is the slurry according to claim 60, and thesecond liquid comprises an additive and water.
 65. The polishing liquidset according to claim 64, wherein the additive is at least one selectedfrom the group consisting of vinyl alcohol polymers and derivatives ofthe vinyl alcohol polymers.
 66. The polishing liquid set according toclaim 64, wherein a content of the additive is 0.01 mass % or greaterbased on a total mass of the polishing liquid.
 67. A polishing liquidcomprising abrasive grains, an additive and water, the abrasive grainsincluding a tetravalent metal element hydroxide, and producing a liquidphase with a nonvolatile content of 500 ppm or greater when an aqueousdispersion with a content of the abrasive grains adjusted to 1.0 mass %has been centrifuged for 50 minutes at a centrifugal acceleration of1.59×10⁵ G, the abrasive grains producing absorbance of not greater than0.010 for light with a wavelength of 450-600 nm in an aqueous dispersionwith a content of the abrasive grains adjusted to 0.0065 mass %.
 68. Thepolishing liquid according to claim 67, wherein the abrasive grainsproduce light transmittance of 50%/cm or greater for light with awavelength of 500 nm in an aqueous dispersion with a content of theabrasive grains adjusted to 1.0 mass %.
 69. The polishing liquidaccording to claim 67, wherein the tetravalent metal element hydroxideis obtained by mixing a tetravalent metal element salt and an alkalisolution.
 70. The polishing liquid according to claim 67, wherein thetetravalent metal element is tetravalent cerium.
 71. The polishingliquid according to claim 67, wherein the additive is at least oneselected from the group consisting of vinyl alcohol polymers andderivatives of the vinyl alcohol polymers.
 72. The polishing liquidaccording to claim 67, wherein a content of the additive is 0.01 mass %or greater based on a total mass of the polishing liquid.
 73. Asubstrate polishing method comprising: a step of placing a film to bepolished, of a substrate which has the film to be polished on itssurface, so as to face an abrasive pad, and a step of polishing at leasta portion of the film to be polished while supplying the slurryaccording to claim 60 between the abrasive pad and the film to bepolished.
 74. A substrate polishing method comprising: a step of placinga film to be polished, of a substrate which has the film to be polishedon its surface, so as to face an abrasive pad, a step of mixing thefirst liquid and second liquid of the polishing liquid set according toclaim 64 to obtain the polishing liquid, and a step of polishing atleast a portion of the film to be polished while supplying the polishingliquid between the abrasive pad and the film to be polished.
 75. Asubstrate polishing method comprising: a step of placing a film to bepolished, of a substrate which has the film to be polished on itssurface, so as to face an abrasive pad, and a step of polishing at leasta portion of the film to be polished while respectively supplying boththe first liquid and second liquid of the polishing liquid set accordingto claim 64 between the abrasive pad and the film to be polished.
 76. Asubstrate polishing method comprising: a step of placing a film to bepolished, of a substrate which has the film to be polished on itssurface, so as to face an abrasive pad, and a step of polishing at leasta portion of the film to be polished while supplying the polishingliquid according to claim 67 between the abrasive pad and the film to bepolished.
 77. The polishing method according to claim 73, wherein thefilm to be polished includes silicon oxide.
 78. The polishing methodaccording to claim 74, wherein the film to be polished includes siliconoxide.
 79. The polishing method according to claim 75, wherein the filmto be polished includes silicon oxide.
 80. The polishing methodaccording to claim 76, wherein the film to be polished includes siliconoxide.
 81. The polishing method according to claim 73, wherein a surfaceof the film to be polished has irregularities.
 82. The polishing methodaccording to claim 74, wherein a surface of the film to be polished hasirregularities.
 83. The polishing method according to claim 75, whereina surface of the film to be polished has irregularities.
 84. Thepolishing method according to claim 76, wherein a surface of the film tobe polished has irregularities.